改性粒状硫酸钙制备及其在聚氯乙烯中的应用

doi:10.19964/j.issn.1006-4990.2022-0267

Abstract

Abstract:

Granular-like CaSO₄（G-CaSO₄） was prepared from phosphogypsum by atmospheric acidification.The effect of the reaction temperature and time on the phase and morphology of G-CaSO₄ were investigated by X-ray diffraction（XRD） and scanning electron microscopy（SEM）.Fourier transform infrared spectroscopy（FT-IR） and transmission electron microscopy（TEM，HR-TEM） analyses were performed on G-CaSO₄ of optimal conditions.Then，G-CaSO₄ was modified with stearic acid to obtain modified granular-like CaSO₄ （MG-CaSO₄），which was used as filler in PVC.The effect of MG-CaSO₄on the micromorphology and mechanical properties of PVC composites were also studied.The results showed that the optimal conditions for the preparation of MG-CaSO₄ were as follows:the reaction temperature was 100 ℃ and the reaction time was 4 h.Under these conditions，G-CaSO₄ with an average particle size of 0.27 μm was successfully prepared，and then modified with 5%（mass fraction） stearic acid to MG-CaSO₄.MG-CaSO₄ was applied to PVC as filler，when the addition amount was 2%，the tensile strength，elongation at break and flexural strength of PVC composites were increased by 11.39%，41.73% and 14.02%，respectively.The research results ccould provide reference for the high-value utilization of phosphogypsum.

Key words: phosphogypsum, atmospheric acidification method, modified granular-like CaSO₄, polyvinyl chloride, mechanical properties

CLC Number:

X705

XU Li, FANG Keneng, BI Yongxiang, YANG Min, CHEN Qianlin. Preparation of modified granular-like CaSO4 and its application in polyvinyl chloride[J]. Inorganic Chemicals Industry, 2023, 55(3): 104-112.

Figures/Tables 12

Table 1

Fig.1

Fig.2

Fig.3

Table 2

Fig.4

Fig.5

Table 3

Fig.6

Fig.7

Fig.8

Fig.9

References 27

1	杜明霞，王进明，董发勤，等.磷石膏资源化利用研究进展[J].矿产保护与利用，2020，40（3）:121-126.
	DU Mingxia， WANG Jinming， DONG Faqin，et al.Research progress on resource utilization of phosphogypsum[J].Conservation and Utilization of Mineral Resources，2020，40（3）:121-126.
2	国亚非，赵泽阳，张正虎，等.磷石膏的综合利用探讨[J].中国非金属矿工业导刊，2021（4）:4-7.
	GUO Yafei， ZHAO Zeyang， ZHANG Zhenghu，et al.Study on comprehensive utilization of phosphogypsum[J].China Non-Metallic Minerals Industry，2021（4）:4-7.
3	崔荣政，白海丹，高永峰，等.磷石膏综合利用现状及“十四五”发展趋势[J].无机盐工业，2022，54（4）:1-4.
	CUI Rongzheng， BAI Haidan， GAO Yongfeng，et al.Current situation of comprehensive utilization of phosphogypsum and its development trend of 14th Five-Year Plan[J].Inorganic Chemicals Industry，2022，54（4）:1-4.
4	母鸿，周贵云，胡海洋.磷矿酸解液制备硫酸钙晶须工艺研究[J].无机盐工业，2022，54（1）:51-55.
	MU Hong， ZHOU Guiyun， HU Haiyang.Study on process of preparing calcium sulfate whiskers from phosphate rock acid hydrolysis solution[J].Inorganic Chemicals Industry，2022，54（1）:51-55.
5	吕智慧，乃学瑛，董亚萍，等.一步常压酸化法制备无水硫酸钙晶须[J].无机盐工业，2017，49（1）:22-24，82.
	Zhihui LÜ， NAI Xueying， DONG Yaping，et al.One-step synthesis of anhydrous calcium sulfate whisker by atmospheric acidification method[J].Inorganic Chemicals Industry，2017，49（1）:22-24， 82.
6	GONG Shang， LI Xiaolong， SONG Fangxiang，et al.Preparation and application in HDPE of nano-CaSO₄ from phosphogypsum[J].ACS Sustainable Chemistry & Engineering，2020，8（11）:4511-4520.
7	李茂刚，陈仕林，雷波.磷石膏晶须生长机理及制备研究进展[J].广州化工，2020，48（17）:15-17.
	LI Maogang， CHEN Shilin， LEI Bo.Research progress on growth mechanism and preparation of phosphogypsum whiskers[J].Guangzhou Chemical Industry，2020，48（17）:15-17.
8	马文静，陈学青，郜丽丽，等.脱硫石膏制备γ-CaSO₄晶须及Ⅱ-CaSO₄晶须[J].高校化学工程学报，2021，35（3）:520-528.
	MA Wenjing， CHEN Xueqing， GAO Lili，et al.Preparation of γ-CaSO₄ and Ⅱ-CaSO₄ whiskers using FGD gypsum[J].Journal of Chemical Engineering of Chinese Universities，2021，35（3）:520-528.
9	徐伟，李梅，张栋梁，等.稀土石膏常压酸化法制备硫酸钙晶须的研究[J].无机盐工业，2020，52（8）:66-71.
	XU Wei， LI Mei， ZHANG Dongliang，et al.Study on preparation of calcium sulfate whisker by atmospheric pressure acidification using rare earth gypsum[J].Inorganic Chemicals Industry，2020，52（8）:66-71.
10	谢晴，蒋美雪，彭同江，等.磷石膏常压酸化法制备无水硫酸钙晶须的实验研究[J].人工晶体学报，2019，48（6）:1060-1066，1071.
	XIE Qing， JIANG Meixue， PENG Tongjiang，et al.Experimental study on preparation of anhydrous calcium sulfate whisker by phosphogypsum at atmospheric acidification method[J].Journal of Synthetic Crystals，2019，48（6）:1060-1066，1071.
11	邓涛，董发勤，刘金凤，等.开放醇水体系制备磷石膏基无水石膏晶须及在丁腈橡胶中的应用探索[J].中国陶瓷，2019，55（9）:23-30.
	DENG Tao， DONG Faqin， LIU Jinfeng，et al.Preparation of phosphogypsum-based anhydrite whiskers by open alcoholic water system and its application in nitrile rubber[J].China Ceramics，2019，55（9）:23-30.
12	MA Fentian， CHEN Chang， WANG Yubin.Mechanical behavior of calcium sulfate whisker-reinforced paraffin/gypsum composit-es[J].Construction and Building Materials，2021，305.Doi:10.1016/j.conbuildmat2021.124795.
13	MA Baoguo， LU Wenda， SU Ying，et al.Synthesis of α-hemihydrate gypsum from cleaner phosphogypsum[J].Journal of Clean- er Production，2018，195:396-405.
14	CHEN Shun， LIU Qiao， HE Xingyang，et al.One-step synthesis of nanoscale anhydrous calcium sulfate whiskers:Direct conversion of calcium carbonate by mixed acid with microemulsion meth-od[J].Journal of Nanoparticle Research，2021，24（1）:1-15.
15	WEI Kailong， DONG Helei， TAN Qiulin，et al.Effect of precursor pH value on the structure and electrical properties of Bi_1.5Zn_1.0Nb_1.5O₇ thin films[J].Ceramics International，2020，46（7）:8700-8705.
16	李强，刘福立，尚超，等.脱硫石膏制备硫酸钙晶须结晶动力学研究[J].人工晶体学报，2018，47（11）:2305-2310.
	LI Qiang， LIU Fuli， SHANG Chao，et al.Study on crystallization kinetics of calcium sulfate whisker prepared by desulfurization gypsum[J].Journal of Synthetic Crystals，2018，47（11）:2305-2310.
17	CHEN Shun， XU Yan， HE Xingyang，et al.Microemulsion synthesis of nanosized calcium sulfate hemihydrate and its morphology control by different surfactants[J].ACS Omega，2019，4（5）:9552-9556.
18	MAO Xiulong， SONG Xingfu， LU Guimin，et al.Control of crystal morphology and size of calcium sulfate whiskers in aqueous HCl solutions by additives:Experimental and molecular dynamics simulation studies[J].Industrial & Engineering Chemistry Research，2015，54（17）:4781-4787.
19	TRITSCHLER U， VAN DRIESSCHE A E S， KEMPTER A，et al.Controlling the selective formation of calcium sulfate polymorphs at room temperature[J].Angewandte Chemie:International Ed.in English，2015，54（13）:4083-4086.
20	岳文香.α-半水磷石膏晶须改性聚乙烯（PE）复合材料的研究[D].贵阳:贵州大学，2017.
	YUE Wenxiang.Study on polyethylene（PE） composites modified by alpha-hemihydrate phosphogypsum whisker[D].Guiyang:Guizhou University，2017.
21	黄宏海，田明，梁文利，等.硬脂酸改性Mg（OH）₂的机理及对EVA性能的影响[J].北京化工大学学报:自然科学版，2006，33（2）:50-54.
	HUANG Honghai， TIAN Ming， LIANG Wenli，et al.Mechanistic studies of the effect of stearic acid coated Mg（OH）₂ on properties of EVA/Mg（OH）₂ composites[J].Journal of Beijing University of Chemical Technology:Natural Science Edition，2006，33（2）:50-54.
22	黄旭，黄健，牛韵雅，等.磷石膏制备的耐热半水硫酸钙晶须表面疏水改性研究[J].硅酸盐通报，2019，38（7）:2021-2027.
	HUANG Xu， HUANG Jian， NIU Yunya，et al.Research on surface hydrophobic modification of heat-resistant calcium sulfate hemihydrate whisker prepared from phosphogypsum[J].Bulletin of the Chinese Ceramic Society，2019，38（7）:2021-2027.
23	KΙSMET Y， DOGAN A.Characterization of the mechanical and thermal prop erties of rape short natural-fiber reinforced thermoplastic composites[J].Iranian Polymer Journal，2022，31（2）:143-151.
24	YUAN Wenjin.Mechanical properties and interfacial interaction of modified calcium sulfate whisker/poly（vinyl chloride） composites[J].Journal of Materials Science & Technology，2016，32（12）:1352-1360.
25	CUI Jiayang.Preparation of a crosslinked chitosan coated calcium sulfate whisker and its reinforcement in polyvinyl chlori-de[J].Journal of Materials Science & Technology，2016，32（8）:745-752.
26	YUAN Wenjin， LU Yunhua， XU Shiai.Synthesis of a new titanate coupling agent for the modification of calcium sulfate whisker in poly（vinyl chloride） composite[J].Materials:Basel，Switzerland，2016，9（8）:625-637.
27	ZHAO Chunyan， LU Yunhua， ZHAO Xuhui，et al.Synthesis of MgCO₃ particles with different morphologies and their effects on the mechanical properties of rigid polyvinyl chloride composit-es[J].Polymer-Plastics Technology and Materials，2021，60（3）:316-326.

原料	化学成分质量分数/%
原料	CaO	SO₃	SiO₂	Al₂O₃	Fe₂O₃	P₂O₅
磷石膏	32.05	42.83	3.45	0.32	0.29	1.82

反应温度/ ℃	FWHM/（º）
反应温度/ ℃	（020）	（012）	（202）	（212）
90	0.164	0.176	0.219	0.238
100	0.162	0.173	0.205	0.228
110	0.153	0.158	0.191	0.201

反应时间/h	FWHM/（º）
反应时间/h	（020）	（012）	（202）	（212）
1	0.191	0.217	0.261	0.328
2	0.180	0.209	0.236	0.298
3	0.179	0.202	0.223	0.271
4	0.162	0.173	0.205	0.228
5	0.179	0.194	0.216	0.255

[1]	LENG Manxi, ZHU Yu, YAN Jikang, XIE Ke, ZOU Yongjie. Study on crystallization characteristics and mineral flotation performance of industrial waste phosphogypsum [J]. Inorganic Chemicals Industry, 2025, 57(3): 108-115.
[2]	TAN Shanyi, WEN Huizi, HE Shuyu, ZHANG Liwen, CHEN Shaohua, XI Benjun. Study on leaching behavior and kinetics of phosphorus from phosphogypsum [J]. Inorganic Chemicals Industry, 2025, 57(2): 105-112.
[3]	TANG Kaijing, LIU Chuanbei, LI Yingding, JIANG Yong, WU Junnan, ZHANG Tao. Research on preparation and mechanism of superhydrophobic phosphogypsum products [J]. Inorganic Chemicals Industry, 2025, 57(1): 97-102.
[4]	LIU Cijun, WU Ziyang, CHENG Shukai, CHEN Xuyong. Effect of recycled fine aggregate on mechanical properties and autogenous shrinkage of ultra-high performance concrete [J]. Inorganic Chemicals Industry, 2024, 56(9): 75-81.
[5]	TANG Xuemei, WANG Meibo, XU Li, ZHANG Xujie, TAI Shijun, YI Xianmei, LIU Hongjuan, PAN Linyi. Study on whitening of phosphogypsum by low⁃temperature calcination [J]. Inorganic Chemicals Industry, 2024, 56(8): 110-115.
[6]	ZHANG Ruijun, CHEN Guoliang, SONG Chuncao, ZHU Yafei. Effects of graphene oxide on mechanical properties and chloride penetration resistance of ultra⁃high performance concrete incorporating recycled sand [J]. Inorganic Chemicals Industry, 2024, 56(8): 54-59.
[7]	SUN Lan, CHEN Shiying, YANG Liuxu, NIU Yiming, ZHAO Aonan. Basic study on fixing soluble phosphorus in phosphogypsum with magnesium slag [J]. Inorganic Chemicals Industry, 2024, 56(8): 92-98.
[8]	HU Cheng, LIU Meng, XIANG Weiheng, CHEN Ping, WANG Neng, LU Guanju, ZHOU Jinlan. Preparation of α-hemihydrous gypsum from CaCl₂ and MgCl₂ and their composite solution [J]. Inorganic Chemicals Industry, 2024, 56(7): 112-117.
[9]	HU Dian, GUO Ze, ZHANG Hanquan, LU Manman. Research on effects of roasting process and typical impurities on reduction and decomposition process of phosphogypsum [J]. Inorganic Chemicals Industry, 2024, 56(7): 88-95.
[10]	HU Cheng, LIU Meng, XIANG Weiheng, DUAN Pengxuan, LI Shunkai, MING Yang, WANG Neng, LU Guanju. Effect of NaCl solution concentration on transcrystallization behavior of α-hemihydrate gypsum from phosphogypsum [J]. Inorganic Chemicals Industry, 2024, 56(6): 87-93.
[11]	TU Yanping, BAI Dengxian, CHENG Shukai, XIE Junjie, HUANG Zhiliang, CHEN Guofu. Effect of high temperature modification of mineral powder and quicklime on properties of phosphogypsum cement based materials [J]. Inorganic Chemicals Industry, 2024, 56(6): 94-101.
[12]	WANG Mingshun, AO Xianquan, YUAN Xing, DONG Wenyan, CHEN Qianlin. Study on effect of crystallizer on preparation of anhydrous calcium sulfate from phosphogypsum [J]. Inorganic Chemicals Industry, 2024, 56(5): 101-107.
[13]	DENG Fuli, XIA Zhixiang, LONG Bingwen, ZHANG Yi, DAI Yafen, WANG Bin, DING Yigang. Study on purification process of phosphogypsum by reverse flotation [J]. Inorganic Chemicals Industry, 2024, 56(5): 115-120.
[14]	WANG Peixiong, GONG Xiaomei, DING Jiaqi, CAO Hong. Effect of crystal modifier on preparation of α-hemihydrates gypsum from industrial gypsum [J]. Inorganic Chemicals Industry, 2024, 56(4): 112-117.
[15]	LI Keke, XUE Jiangwei, WANG Luwei, GUAN Xuemao. Effect of MgAl-layered double hydroxides on properties of high-iron low-calcium portland cement [J]. Inorganic Chemicals Industry, 2024, 56(4): 57-63.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Preparation of modified granular-like CaSO4 and its application in polyvinyl chloride

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 27

Related Articles 15

Metrics

Comments

Recommended 0